Detergent compositions containing ouaternary ammonium derivatives of n n&#39;-substituted 4 4&#39;-bis(benzimidazol-2-yl)stilbenes

ABSTRACT

N,N&#39;&#39; - SUBSTITUTED 4,4&#39;&#39; - BIS(BENZIMIDAZOL - 2 -YL)STILBENES ARE INTERACTED WITH ALKYLATING AGENTS TO PRODUCE QUATERNARY AMMONIUM COMPOUNDS WHICH ARE USEFUL, PARTICULARLY FOR INCORPORATION IN DETERGENT COMPOSITIONS, FOR CONCOMITANTLY DISINFECTING AND WHITENING OR BRIGHTENING TEXTILE MATERIALS.

United States Patent 0 3,642,642 DETERGENT COMPOSITIONS CONTAINING QUATERNARY AMMONIUM DERIVATIVES 0F N,N-SUBSTITUTED 4,4'-BIS(BENZIMID- AZOL-2-YL)STILBENES Nathan N. Crouuse, Cincinnati, Ohio, assignor to Sterling Drug Inc., New York, NY.

No Drawing. Original application Aug. 1, 1967, Ser. No. 657,515, now Patent No. 3,583,984. Divided and this application Sept. 23, 1970, Ser. No. 74,938

Int. Cl. Clld 1/18, 3/26 US. Cl. 252-543 10 Claims ABSTRACT OF THE DISCLOSURE N,N' substituted 4,4 bis(benzimidazol 2 yl)stilbenes are interacted with alkylating agents to produce quaternary ammonium compounds which are useful, particularly for incorporation in detergent compositions, for concomitantly disinfecting and whitening or brightening textile materials.

This is a division of my copending application Ser. No. 657,515, filed Aug. 1, 1967, now Pat. No. 3,583,984.

This invention relates to novel deteregnt compositions containing certain fluorescent compounds of the benzimidazolylstilbene series useful as disinfecting agents and as whitening and brightening agents.

In my prior copending application, Ser. No. 657,515, there are described and claimed the quaternary ammonium derivatives of benzimidazolylstilbenes useful in practicing the present invention. My said prior invention provides new fluorescent whitening and brightening agents having antibacterial and antifungal properties which are useful in the treatment of threads, sheets, films, filaments, textile fabrics, and the like, as well as in the manufacture of paper, varnishes, inks, coatings, and plastics, These new compounds are particularly well adapted to application to white and colored fabrics, since they are substantive even in low concentrations to a Wide variety of natural and synthetic fibers. They impart a desirable blue white hue to white fibers and brighten colored fibers treated therewith, while at the same time imparting an antibacterial and antifungal finish to the fibers.

The whitening and brightening agents useful in preparing the detergent compositions of this invention are quaternary ammonium salts of the benzirnidazolylstilbene series having the structure of Formula I shown below,

Formula I where R R R and R are hydrogen, lower alkyl having 1 to 4 carbon atoms, lower alkoxy having 1 to 4 carbon atoms, or halo; Y and Y are lower alkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6 carbon 3,642,642 Patented Feb. 15, 1972 atoms, 2-hydroxy-3-sulfopropyl, hydroxy-oxaalkyl having 3 to 15 carbon atoms, carboxy-lower alkyl having 2 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbon atoms, phenyl-lower alkyl having 7 to 11 carbon atoms, allyl or methallyl; Z and Z are lower alkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6 carbon atoms, carboxy-lower alkyl having 2 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbon atoms, phenyllower alkyl having 7 to 11 carbon atoms, allyl, methallyl, or 3-halo-2-propenyl; and An is an anion.

When R R R and R represent lower alkyl having 1 to 4 carbon atoms, for example, there are included methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and the like. When Y Y Z and Z represent lower alkyl having 1 to 6 carbon atoms, for example, there are included methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-amyl, n-hexyl and the like. When R R R and R represent lower alkoxy having 1 to 4 carbon atoms, there are included for example, methoxy, ethoxy, n-butoxy, and the like. When Y Y Z and Z represent hydroxy-lower alkyl having 2 to 6 carbon atoms, there are included for example, 2-hydroxyethyl,1-methyl-2-hydroxyethyl and 2,3-dihydroxypropyl, and the like. When R R R and R represent halo, for example, there are included chloro, bromo and fiuoro.

When representing hydroxy-oxaalkyl, having 3 to 15 carbon atoms, the groups Y and Y include for example, 2 hydroxy 3 (2,3 dihydroxypropoxy)propyl, 2-hydroxy 3 (2 hydroxyethoxy)propyl, 1 methyl-2-(1- methyl-Z-hydroxyethoxy)ethyl, 2 hydroxy 3 [2-(2- hydroxyethoxy)ethoxy]propyl, and the like.

When Y Y Z and Z represent carboxy-lower alkyl having 2 to -6 carbon atoms, there are included for example, carboxymethyl, 2-carboxyethyl, and S-carboxypentyl. When Y Y Z and Z represent cyano-lower alkyl having 2 to 6 carbon atoms, there are included for example, 2-cyanoethyl, S-cyanopropyl, and S-cyanopentyl.

The term phenyl-lower alkyl as used herein means a monovalent hydrocarbon radical consisting of phenyl bonded to one of the valences of a divalent lower-alkylene radical having one to four carbon atoms as exemplified by, but not limited to methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, and the like. Thus, solely for illustration and Without limitation, examples of phenyl-lower alkyl are benzyl, l-phenylethyl, 2-phenylethyl, 3-phenylpropyl, and the like.

The term anion, as used herein, means the anion of any salt-forming inorganic or organic acid. The choice of an anion is not critical in the operation of the preparative processess nor is the identity of the anion a critical feature of the claimed compositions. Accordingly, by way of illustration and without limitation thereto, the anions can be for example, bromide, chloride, iodide, fluoride, nitrate, sulfate, phosphate, acetate, formate, ptoluenesulfonate, phenoxyacetate and the like. When a pharmaceutical use is intended, it is preferred to employ anions of pharmaceutically-acceptable salt-forming inorganic or organic acids since the disinfecting properties of the quaternary ammonium compounds of this invention make them applicable to human or animal use. Thus, such an acid is one whose anions are non-toxic and innocuous to the animal organism in effective concentration of the quaternary ammonium salts so that beneficial properties inherent in the common structural entity are not vitiated by side-effects ascribable to the anion.

In general, the compounds of the above structure are high-melting white or yellow solids. They are generally soluble in water and the lower-alkanols and are insoluble in hydrocarbons, halogenated hydrocarbons, ketones, and

O ethers. They are moderately soluble in N,N-dimethylformamide and dimethyl sulfoxide and some of them are soluble in acetic acid.

When the above-described compounds are dissolved in aqueous media, they fiuoresce blue-white under ultraviolet light and show a wide range of absorption in the ultraviolet region. They are substantive to a wide variety of natural and synthetic fibers, for example, cotton, cellulose acetate, viscose rayon, nylon, silk, and polyacrylonitrile (Orlon-Du Font) and are absorbed by such fibers even from very low concentrations in aqueous solutions. The compounds have relatively high stability to sunlight, synthetic detergents, and chlorine-containing bleaching agents.

The above-described properties of these quaternary benzimidazolium compounds make them especially valuable as whitening and brightening agents in treating white and colored fabrics to neutralize the yellowness in white textiles or to enhance the brilliance of colored textiles. In such utilization, the relatively high resistance of the compounds to chlorine bleaching and to light are distinct advantages, since many of the previously known whitening and brightening agents of the stilbene series have had as their chief drawbacks a lack of resistance to chlorine-containing bleaching agents and ease of decomposition under influence of light.

A further important advantage of the preferred species of these quaternary benzimidazolium compounds lies in the fact that on repeated applications to white fabrics, thereby building up the amount of the whitening agent on the fibers, the fabrics remain bluish-white and do not develop undesirable discoloration, for example a red or gray color, such as is produced by many of the known optical bleaching agents when they are applied repeatedly, as for instance in successive launderings.

The compounds described herein are of unique value, because in addition to their usefulness as whitening agents, they also have biostatic properties and are useful as antibacterial and antifungal agents. Thus, when tested by standard serial dilution procedures, these compounds were found to have bactericidal, bacteriostatic, fungicidal, and fungistatic activity in vitro. More specifically the quaternary benzimidazolium compounds have been found to possess antibacterial activity toward Staphylococcus aureus 209, Salmonella typhosa Hopkins, Bacterium ammoniogenes, Closlridium welclzii M., and Pseudomonas aeruginosa 211. They also posses antifungal activity toward Trichophyton mentagrophytes, Aspergillus niger and Monilia albicans. The substantivity of these compounds to a variety of textiles together with the abovementioned activities provide a means of imparting longlasting antibacterial and antifungal properties as well as brightening or whitening effects to fibrous materials. For

example, it has now been found that textile materials, which undergo successive launderings wherein the abovedescribed compounds are employed as mentioned hereinbefore, have the property of markedly inhibiting the growth of bacteria and of destroying existing bacteria.

The treatment of textile fabrics with these compounds is readily carried out by conventional procedures. For example, an aqueous solution containing about 0.0001 to 0.5% by weight of the compound is applied to the fabric, which absorbs the fluorescent compound and is whitened or brightened beneficially thereby. This application of the compound can be conveniently carried out in conjunction with a rinsing or washing operation.

A convenient mode of using and marketing these quaternary benzimidazolium compounds is by incorporating them into solid or liquid detergents in an appropriate concentration, for example 0.02 to 0.5% by weight. Nonionic detergents are preferred for this purpose. However, anionic and cationic detergents can be employed without adversely affecting the germicidal or whitening and brightening properties of the quaternary benzimidazolium compounds.

The compounds useful in the practice of this invention can be prepared by employing as starting materials appropriate 4,4'-bis-(benzimidazol-Z-yl)stilbenes. In general,

I have found that it is convenient to start with the compounds having the structural formula Formula II wherein R R R and R have the previously-given meanings.

The N,N-unsubstituted compounds (Formula II) react readily with alkylating agents to yield symmetrical or unsymmetrical N,N-di(alkyl or substituted alkyl) derivatives. The substituting groups are alkyl or substituted alkyl radicals of the type hereinbefore defined as Y and Y in Formula I. The alkylating reaction is readily carried out as described in United States Pat. 2,838,504, viz. by heating a 4,4'-bis(benzimidazol-Z-yl)stilbene with the appropriate alkylating agent. The N,N-disubstituted intermediates having the structural formula Formula III wherein Y and Y have the same meanings given hereinbefore, are then further caused to react with the same or different alkylating agents to produce the quaternary benzimidazolium salt compounds described above. The compounds of Formula I, wherein Y =Y =Z :Z can be prepared without isolation of the N,N-disubstituted intermediate by reacting the appropriate N,N-unsubstitutcd compound of Formula II with an excess of alkylating agent over the stoichiometrically-required four molecular equivalents.

The 4,4-bis(benzimidazol-Z-yl)stilbenes of Formula II used as starting materials as described above are known in the prior art and are described with their preparation in United States Pat. 2,838,504. They are prepared by cyclization of a bis(ortho-aminoanilide) of a 4,4-stilbenedicarboxylic acid by heating it under acidic conditions. For example, the following compounds of Formula II are useful starting materials for preparing the quaternary ammonium salt compounds described above. (As will be appreciated, the tautomerism of these products affords in many cases alternative choices of designation for a single substance; these choices are indicated hereinbelow,

where appropriate, in accordance with conventional nomenclature requirements):

4,4-bis (benzimidazol-Z-yl stilbene;

4,4'-bis [4( or 7 -methoxybenzimidazol-Z-yl] stilbene;

4,4'-bis [4 (or 7 -ethoxybenzimidazole-2-yl] stilbene;

4,4-bis [5 (or 6 -isopropoxybenzimidazol-Z-yl] stilbene;

4,4-bis (5,6-dimethoxybenzimidazol-2-yl) stilbene 4,4'-bis (5 ,6-dibutoxybenzirnidazol-Z-yl stilbene;

4,4'-bis [4,5,7 (or 4,6,7 -trimethoxybenzimidazol-2-yl] stilbene;

4,4'-bis [4 (or 7) -methylbenzimidazol-2-yl] stilbene;

4,4'-bis 5 (or 6) -tert-butylbenzimidazol-2-yl]stilbene;

4,4'-bis 5 ,6-dimethylbenzimidazol-Z-yl stilbene;

4,4'-bis 4,5 ,6,7-tetramethylbenzimidazol-Z-yl) stilbene;

4,4-bis [5 (or 6) -ethylbenzimidazol-2-yl] stilbene;

4,4'-bis[5 (or 6) -chlorobenzimidazol-2-yl] stilbene;

4,4'-bis [5 (or 6) -fluorobenzimidazol-2-yl] stilbene;

4,4'-bis [4,6 (or 5,7) -dibromobenzirnidazol-2-yl] stilbene;

4,4-bis [4,5,6 (or 5,6,7 -trichlorobenzimidazol-Z-yl] stilbene 4,4-bis [6-methoxy-5-fluoro (or 5-methoxy-6-fluorobenzimidazol-Z-yl] stilbene;

4,4-bis [4-bromo-6,7-methylenedioxy( or 7-bromo-4,5- methylenedioxy) benzimidazol-2-yl] stilbene; and

4,4'-bis 5-methoxy-6-methyl(or 5 -methyl-6-methoxy) benzimidazol-Z-yl] stilbene.

The alkylating agents useful in this conversion are well known in the prior are and are esters of strong organic and inorganic acids having the formula Z-An, where Z is a member of the class consisting of lower alkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6 carbon atoms, 2-hydroxy-3-sulfopropyl, hydroxy-oxaalkyl having 3 to carbon atoms, carboxylower alkyl having 3 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbon atoms, and phenyl-lower alkyl having 7 to 11 carbon atoms; and An is an anion as hereinbefore defined. Illustrative of these esters are: methyl sulfate, ethyl sulfate; methyl p-toluenesulfonate; lower alkyl halides, for example methyl chloride, ethyl bromide, butyl chloride, and hexyl chloride; phenyl-lower alkyl halides, for example benzyl chloride, p-methoxybenzyl chloride, o-chlorobenzyl chloride, 2-chloro4 methoxybenzyl bromide, and benzyl bromide; allyl and methallyl halides, for example allylchloride and methallyl bromide; carboxyl-lower alkyl halides, for example Z-carboxyethyl chloride and carboxymethyl bromide; cyano-lower alkyl halides, such as 2-cyanoethyl chloride; hydroxylower alkyl halides, such as 2,3-dihydroxypropyl chloride (or glycerol alpha-chlorohydrin), ethylene chlorohydrin, ethylene bromohydrin, isobutylene chlorohydrin; 2-hydroxy-3-sulfopropyl chloride or bromide; hydroxyoxaalkyl halides, for example 2-hydroxy-3-(2-hydroxyethoxy)propyl chloride, 2-hydroxy 3 (2,3-dihydroxypropoxy)propyl chloride and 2-hydroxy-3-[2-(2-hydroxyethoxy)ethoxy]propyl chloride. Also useful as alkylating agents are 1,2-lower alkylene oxides having 2 to 6 carbon atoms, for example, ethylene oxide, propylene oxide, glycidol, and epichlorohydrin; and acrylonitrile and methacrylonitrile.

The substitution of simple moieties in the benzene rings of the starting materials used in the processes abovedescribed, i.e. in the phenyl-lower alkyl alkylating agents and in the stilbene moiety of the compounds of Formula II, for example, halo (viz. chloro, bromo and fluoro), alkyl, lower alkoxy, lower alkylsulfonyl, lower alkylsultiny, nitro, and trifluoromethyl, does not interfere with the operability of the process, and the resulting quaternary benzimidazolium compounds correspondingly substituted in said benzene rings thereof have the same utility as, and are the full equivalents of, the compounds herein described.

The chemical structures of the above-described compounds were established by their mode of synthesis and are corroborated by the correspondence between calculated values for the elements and values found by chemical analysis and by concordant spectral properties.

The following procedures and examples will further illustrate specific embodiments of the invention without the latter being limited thereto.

PRODUCTS AND PROCESSES Example 1 To a stirred solution of 24.6 (0.05 mole) of 4,4'-bis (1-allylbenzimidazol-2-yl)stilbene in 137.5 ml. of 2-rnethoxyethanol at 105 C. there was added dropwise, over a period of thirty minutes, 31.2 g. (0.22 mole) of methyl iodide. The mixture was stirred at a temperature between and 105 C. for two hours and then the solvent removed in vacuo. Acetone was added to the residue. The solid was collected by filtration and washed with fresh acetone. Recrystallization from boiling methanol gave 4,4'stilbenebis(l allyl 3 methyl 2 benzimidazolium iodide) a yellow powder, M.P. 296-297" C. (dec.) (corn).

Example 2 A stirred mixture of 21.0 g. (0.043 mole) of 4,4-bis (1-allylbenzimidazol-2-yl)stilbene and 118 ml. of 2-ethoxyethanol was heated to reflux. To the solution thus formed there was added at 105 C. dropwise over a period of forty-five minutes, 140 g. (1.02 mole) of n-butyl bromide. The mixture was then stirred and heated at a temperature between '95 and 105 C. for a total of twentyeight hours with the addition as needed of small quantities of anhydrous sodium carbonate (for neutralizing acid resulting from solvolysis). The reaction mixture was cooled and the solid that separated was filtered oif, washed with fresh 2-ethoxyethanol, and then with acetone. The solid was recrystallized from boiling n-butanol to obtain 4,4'-stilbenebis(l allyl-3-n-butyl-2-benzimidazolium bromide) was as a beige-colored solid, M.P. 272.0273.2 C. (dec.) (corr.).

Example 3 Following the procedure of Example 1 hereinabove, but substituting allyl bromide in molecular equivalent amount for the methyl iodide used in that procedure, there was obtained 4,4'-stilbenebis(1,3-diallyl-2-benzimidazolium bromide), which after recrystalilzation from boiling anhydrous ethyl alcohol was a yellow powder, M.P. 284 C. (dec.) (corn).

Example 4 To a stirred solution of 24.6 (0.05 mole) of 4,4'-bis (l-allylbenzimidazol-Z-yl)stilbene in 137 ml. of 2-ethoxyethanol at 1.05 C. there was added dropwise over a period of ten minutes 12.2 g. (0.11 mole) of 1,3-dichloropropene. Stirring and heating at a temperature between 95 and a C. were continued for a total of 57 hours during which period there was added an additional 24.0 g. (0.216 mole) of 1,3-dichloropropene and small quantities of 35% aqueous sodium hydroxide solution as needed (for neutralizing acid resulting from solvolysis). The solvent was evaporated in vacuo and acetone was added to the residue. The solid was collected, washed with fresh acetone and recrystallized from benZene/n-butyl alcohol to obtain 4,4'-stilbenebis[1-allyl-3-(3-chloro 2 propenyl)-2-benzimidazolium chloride], an off-white solid, M.P. 252253 C. (dec.).

Example 5 A solution of 24.6 g. (0.05 mole) of 4,4'-bis(1-allylbenzimidazol-Z-yl)stilbene in 137.5 ml. of Z-methoxyethanol was stirred and heated at 'C. while during a period of fifteen minutes a solution of 35.4 g. (0.22 mole) of 4-chlorobenzyl chloride in 25 ml. of Z-methoxyethanol was added dropwise. Stirring and heating at a temperature between 95 and 105 C. were continued for three hours. The solvent was evaporated under reduced pressure, and acetone was added to the residue. The solid that separated was collected, washed with fresh acetone and then recrystallized from 2-methoxyethanol/acetone with the aid of decolorizing charcoal to obtain 4,4-stilbenebis[1-allyl 3 (4 chlorobenzyl)-2-benzimidazolium chloride], a pale yellow solid, M.P. 205.5 (froth)206.5 C. (dec.) (corr.).

Example 6 To a stirred solution of 14.8 g. (0.03 mole) of 4,4-bis (1-allylbenzimidazol-2-yl)stilbene in 82.5 ml. of 2-methoxyethanol heated at a temperature between 95 and 100 C. there was added over a period of twenty minutes, 22.8 g. (0.106 mole) of powdered 4-nitrobenzyl bromide. The mixture was stirred and maintained at a temperature between 95 and 100 C. for a period of one and threequarter hours. Approximately three-fourths of the solvent was evaporated under reduced pressure and acetone was added to the residue. The suspension was chilled at C. for thirty minutes and the solid that separated was collected, washed with fresh acetone and dried at 75 C. to obtain 4,4-stilbenebis[1-allyl-3-(4-nitrobenzyl)-2-benzimidazolium bromide], a yellow solid, M.P. 249.2262 C. (dec.) (corr.).

Example 7 Employing the procedure of Example 5 above, 49.2 g. (0.1 mole) of 4,4-bis(l-allylbenzimidazol-2-yl)stilbene in 275 ml. of 2-methoxyethanol was treated with a solution of 43.0 g. (0.22 mole) of mixed (2,5 isomer=50%; 2,4 isomer=37%; 3,4 isomer=13%) dichlorobenzyl chloride in 25 ml. of 2-methoxyethanol to obtain 4,4-stilbenebis [1-allyl-3- (dichlorobenzyl)-2-benzimidazolium chloride], a yellow solid.

Example 8 Following the procedure of Example 1 hereinabove, 25.0 g. (0.051 mole) of 4,4-bis(1-allylbenzimidazol-2-yl) stilbene and 29.9 g. (0.1 mole) of 2,3,4,5,6-pentachlo.ro benzyl chloride was interacted in 125 ml. of 2-methoxyethanol. There was thus obtained 4,4'-stilbenebis[l-allyl- 3-(2,3,4,5,6-pentachlorobenzyl)-2-benzimidazoliurn chloride], a yellow solid.

Example 9 Using the procedure of Example 5 hereinabove, but substituting 4-dodecylbenzyl chloride for 4-chlorobenzyl chloride used in that example, there was obtained 4,4- stilbenebis[1-allyl 3 (4-dodecylbenzyl)-2-benzimidazolium chloride], a yellow solid, M.P. 103-105 C.

Example 10 (A) Alkylation of 4,4'-bis(benzi1nidazol-2-yl)stilbene with ethylene oxide. A mixture of 550 g. (1.33 moles) of 4,4'-bis(benzimidazol-Z-yl)stilbene, 2.68 liters of 95% ethanol and 174 g. (4.35 moles) of sodium hydroxide pellets was heated at 76-86 C. and 540 g. of ethylene oxide was passed into the resulting solution over a period of six hours. At this point, 141 g. (2.35 moles) of glacial acetic acid was added to the solution dropwise during a period of fifteen minutes. During a period of four hours an additional 181 g. of ethylene oxide was passed into the solution. The reaction mixture was then poured in a thin stream into a rapidly agitated solution of 196.5 g. of sodium chloride in 19.65 liters of water at 30 C. The mixture was stirred for thirty minutes and the precipitated solid was collected by filtration. The solid was washed with fresh Water until free of alkali. There was thus obtained after drying to constant weight 664.5 g. of product which was chiefly a mixture of 4,4'-bis[1-(2-hydroxyethyl)benzimidazol-Z-yl]stilbene, 4-[1-(2-hydroxyethyl)benzimidazol 2 yl]-4'-{1-[2-(2-hydroxyethoxy) ethyl]benzimidazol-Z-yl}|stilbene and 4,4-bis{1-[2-(2- hydroxyethoxy ethyl] benzimidazol-Z-yl}stilbene.

(B) A solution of 45.0 g. of the mixture of hydroxyethylated products obtained as described above, and 225 ml. of 2-methoxy-ethanol was heated at reflux during a period of fifteen minutes. The temperature was lowered to C. and during twenty-five minutes a solution of 19.0 g. (0.157 mole) of allyl bromide in 19.0 ml. of Z-methoxyethanol was added dropwise. The mixture was refluxed for two and one-half hours and then concentrated by distilling oil? a portion of the solvent. To the cooled residue there was added 200 ml. of acetone and the solid that separated was collected. The solid was dissolved in ml. of boiling 95% ethanol and the solution chilled. A solid separated and was removed by filtration. The alcohol filtrate was then poured into 1 liter of acetone at 8-10 C. and the mixture further diluted with 500 ml. of acetone. The mixture was stored in a refrigerator overnight and the solid that separated was collected by filtration, washed with 200 ml. of acetone, and dried to constant weight to obtain chiefly 4,4'-stilbenebis {1-[2-(2- hydroxyethoxy)ethyl]-3-allyl 2 benzimidazolium bromide}, melting at 140-145 C. with decomposition.

Example 11 Following the procedure described in Example 10 hereinabove, but substituting 24 g. (0.149 mole) of 4- chlorobenzyl chloride for the 19 g. of allyl bromide used in that example, there was obtained chiefly 4,4-stilbenebis {1-[2-(2-hydroxyethoxy)ethyl] 3 (4-chlorobenzyl)- 2-benzimidazolium chloride}, a tan solid, melting at C. with decomposition.

Example 12 With stirring, 27.5 g. of the mixture of hydroxyethylated products obtained as described above was dissolved in 275 ml. of refluxing Z-methoxyethanol. The temperature of the solution was lowered to 75 C. and 19.5 g. (0.10 mole) of 3,4-dichlorobenzyl chloride was added dropwise during fifteen minutes. Reflux was reestablished and was continued for four hours. The mixture was cooled in a refrigerator overnight. Then 200 ml. of diethyl ether was added to the stirred mixture. A solid separated and was collected by filtration. The solid was washed with fresh ether and dried in a vacuum desiccator to obtain as a yellow solid, a mixture comprised chiefly of 4,4- stilbenebis 1- (2-hydroxyethyl)-3- (3,4 dichlorobenzyl)- 2-benzimidazolium chloride] and 4-[1-(2-hydroxyethyl) benzimidazol-Z-yl] 4' {1-[2-(2-hydroxyethoxy)ethyl] benzimidazol-Z-yl} stilbene N ,N '-bis(3,4-dichlorobenzyl chloride).

Example 13 Using the procedure of Example 12 hereinabove, but substituting 2,4-dichlorobenzyl chloride for 3,4-dichlorobenzyl chloride used in that example, there was obtained as a yellow solid a mixture comprised chiefly of 4,4-stilbenebis[1-(2-hydroxyethyl) 3 (2,4-dichlorobenzyl)-2- benzimidazolium chloride] and 4-[1-(2-hydroxyethyl) benzimidazol-Z-yl] 4' {1-[2-(2-hydroxyethoxy)ethyl] benzimidazol-Z-yl} stilbene N ,N -bis(2,4-dichlorobenzyl chloride).

Example 14 Following the procedure described in Example 12 hereinabove, but substituting 2,3,4,5,6-pentachlor0benzyl chloride for the 3,4-dichlorobenzyl chloride used in that example, there was obtained as a mustard-colored powder a mixture comprised chiefly of 4,4'-stilbenebis[3-(2,3,4,5, 6-pentachlorobenzyl)-1-(2-hydroxyethyl) 2 benzimidazolium chloride] and 4-[1-(2-hydroxyethyl)benzimidazol 2 yl]-4-{1-[2-(2-hydroxyethoxy)ethyl]benzimidazol-Z-yl} stilbene N ,N '-bis(2,3,4,5,6-pentachlorobenzyl chloride).

Example 15 (A) Alkylation of 4,4'-bis(benzimidazol-Z-yl)stilbene with propylene oxide.A mixture of 61.5 g. (0.15 mole) of 4,4'-bis(benzimidazol-Z-yl)stilbene, 321 ml. of ninetyfive percent ethyl alcohol, and 47.5 g. of a 50% aqueous solution of sodium hydroxide was heated at reflux for thirty minutes to etfect solution. The temperature was then lowered to 75 C. and during a period of four hours a total of 102 g. (1.76 moles) of propylene oxide was added in small portions. Heating at reflux was continued for a period of several hours and the mixture was then cooled. A solid had separated. The mixture was filtered and the solid thus collected was Washed in a solution of 160 ml. of ethyl alcohol and 6.7 ml. of a 50% aqueous solution of sodium hydroxide. The solid was then further washed with ethyl alcohol and dried to constant weight in a vacuum oven. There was thus obtained 58.7 g. of product as a yellow-gray powder which was chiefly a mixture of 4,4'-bis[ 1-( 1-methyl-2-hydroxyethy1)benzimidaZol-2-yl] stilbene and 4-[1-(1-methyl 2 hydroxyethyl) benzimidazol-Z-yl]-4-{1-[l-methyl 2 (2,3-dihydroxypropoxy)ethyl]benzimidazol-Z-yl} stilbene.

(B) With stirring, 25.4 g. of the mixture of hydroxypropylated products obtained as described above, and 125 ml. of Z-methoxyethanol were heated together at 80 C. while during a period of fifteen minutes a solution of 17.0 g. (0.105 mole) of 4-chlorobenzyl chloride in 17.0 ml. of 2-methoxyethanol was added dropwise. The mixture was refluxed for forty-eight hours and after cooling, filtered to remove a small amount of undissolved solid. The filtrate was diluted with 1.5 liters of diethyl ether causing a solid to separate. The mixture was set aside overnight, and the solid was collected by filtration, washed with diethyl ether and dried to obtain chiefly 4-[1-(1-methyl-2- hydroxyethyl)benzimidazol-2-yl] 4' {1 [1 methyl- 2 -(2,3 dihydroxypropoxy)ethyl]benzimidazol 2 yl} stilbene N ,N -bis(4-chlorobenzyl chloride).

EXAMPLE 16 A mixture of 10.5 g. (0.025 mole) of 4,4-bis(benzimidazol-2-yl)stilbene and 110 g. (0.86 mole) of benzyl chloride was stirred and heated at reflux for a total of twenty-one hours. The mixture was filtered, and the collected solid was washed with benzene, and dried in a vacuum oven. Recrystallization of the solid from boiling 95% ethanol with the aid of decolorizing charcoal gave 4,4'-stilbenebis(1,3-dibenzy1-2-benzimidazolium chloride) as the trihydrate, an off-white solid, M.P. 254.0260.3 C. (dec.) (corn).

EXAMPLE l7 Forty-five grams of the mixture of hydroxyethylated products obtained as described above (Example 10A) was dissolved in 200 ml. of refluxing 2-methoxyethanol. The temperature of the solution was lowered to 100 C. and 6.7 g. (0.038 mole) of u,u'-dichloro-p-xylene was added over a period of five minutes. Reflux was reestablished and was continued for four hours. The mixture was set aside overnight at room temperature, and then was filtered to remove a small amount of insoluble material. The filtrate was diluted with 1.4 liters of diethyl ether causing a gum to separate. The ether was decanted from the gum and 300 ml. of fresh diethyl ether was added to the gum. Manual working of the gum produced a powdery solid which was collected, washed with fresh diethyl ether and dried to obtain a mustard-colored powder having the structural formula:

and chemically named as a bis((2 4 {1 [2 (2- hydroxyethoxy)ethyl]benzimidazol 2 yl}stilbenyl 4 1 [2 (2 hydroxyethoxy)ethyl] 3 benzimidazolium) )-p-xylene dichloride.

When the procedures of Examples 1, 2, 3, 4, 5, 6, 10B, 12, 15B, 16, or 17 are followed in reacting the appropriate N,N'-substituted or unsubstituted 4,4'-bis(benzimidazol-2-yl)stilbene with the appropriate alkylating agent as defined hereinbefore there are obtained:

4,4-stilbenebis 1-allyl-3-ethyl-2-benzimidazolium bromide) 4,4'-stilbenebis( 1-al1yl-3-n-propyl-2-benzimidazolium bromide) 4,4'-bis( l-allylbenzimidazol-Z-yl) stilbene N -methobr0mide-N '-n-buty1 bromide;

4,4'-stilbenebis[ 1-allyl-3-methyl-4(o r 7 -methoxy-2- benzimidazolium iodide];

4,4-stilbenebis[1allyl-3-(4-chlorobenzyl)-5,6-

dibutoxy-Z-benzimidazolium chloride];

4,4-bis[1-(Z-carboxyethyl)benzimidazol-Z-yl]stilbene N -n-hexyl chloride-N '-isopropyl chloride;

4,4-stilbenebis[1-(2,3-dihydroxypropyl)-3-(benzyl)- Z-benzimidazolium chloride];

4,4'-stilbenebis l- 2-cyanoethyl -3 -benzyl-2-benzimidazolium chloride] 4,4-stilbenebis l-(4-methoxyphenethyl -3-methallyl- 2-benzimidazolium bromide];

4,4'-stilbenebis[ l 4-methylbenzyl -3- (2-chloro-4- methoxybenzyl) -4,7-diethoxy-2-benzimidazolium bromide] 4,4-stilbenebis 1-(2-hydroxy-3-sulfopropyl) -3- (4-chlorobenzyl) -2-benzimidazolium chloride] 4-[ l-methyl- (5 or 6 -chlorobenzimidazol-2-yl]-4'-[ 1- ethyl- (5 or 6 -chlorobenzimidaZ01-2-yl] stilbene N ,N '-bis( methylsulfate);

4,4'-stilben ebis[1-(2-hydroxyethy1)-3-(4-methylbenzyl)- 5 ,6-dimethyl-2-benzimidazolium chloride];

4,4'-stilbenebis{ l- [2- Z-hydroxyethoxy) ethyl] -3- (2,5-dichlorobenzyl -5 (or 6 -tert-butyl-2-benzimidazolium chloride};

4,4'-stilbenebis[ 1- 2,4-dichlorobenzyl -3- 4-dodecy1- benzyl) -5 (or 6 )-chloro-2-benzimidazolium chloride] 4,4'-stilbenebis l 3-methylbenzyl) -3- 3-bromopropenyl)-5 (or 6)-chloro- -benzimidazolium bromide];

4,4'-stilbenebis l- 2,3-dihydroxypropyl -3-n-butyl- 2-benzimidazolium chloride];

4,4'-stilbenebis 1- (2-carboxyethyl) -3-methallyl-2- benzimidazolium chloride];

4,4'-stilbenebis l- 2-hydroxyethyl -3-rnethallyl-5,6-dimethyl-Z-benzimidazolium chloride];

4,4'-stilbenebis[1-(2-hydroxy-3-sulfopropyl)-3- phenethyl-Z-benzimidazolium chloride];

4,4-st1lbenebis{ 1- [2- (2-hydroxyethoxy) ethyl] -3 -benzyl-5 (or 6)-tert-butyl-2-benzimidazolium chloride};

4,4'-stilbenebis 1- 2-cyanoethyl)-.3-carboxymethyl-2- benzimidazolium chloride];

4,4'-stilbenebis{1-[2-hydroxy-3- 2,3-dihydroxypropoxy) propyl] -3-methyl-2-benzimidazolium iodide};

4,4-stilbenebis{ l- .2-hydroxy-3- [2- 2-hydroxyethoxy) ethoxy]propyl -3-benzyl-2-benzimidazolium chloride}:

4,4'-stilbenebis[ 1-(2-carboxyethyl) -3-(4-fluorobenzyl)- 2-benzimidazolium chloride];

4,4'-stilbenebis( 1-a1ly1-3-n-butyl-4,5 ,6,7-tetramethyl-2- benzimidazolium bromide);

4,4'-stilbenebis[ 1-(2-cyanoethy1)-3 benzy1 6-methoxy-5- fiuoro (or 5-methoxy-6-fluoro) -2-b enzimidazolium bromide] 4- 1-c'arboxymethylbenzimidazol-2-yl) -4'- l-methylbenzimidazol-Z-yl) stilbene N N '-bis (4-bromobenzyl bromide) 4,4'-stilbenebis 1-(2-cyanoethyl) -3-isopropyl-2- benzimidazolium 'bromide] 4-[ l- (Z-carboxyethyl) benzimidazol-Z-yl] -4- l-methylbenzimidazol-Z-yl) stilb ene N N '-bis (methallyl chloride) 1 1 4,4-stilbenebis l- (2-chlorobenzyl -3- 2-hydroxy-2- sulfopropyl )-2-benzimidazolium chloride]; and 4-( 1-methylbenzimidazol-2-yl -4'-{ l- [2-hydroxy-3- (2- hydroxyethoxy propyl] benzimidazol-Z-yl}stilbene N N '-bis 3-methylb enzyl bromide) As will be evident to the skilled chemist, the mixtures obtained in the alkylation of 4,4'-bis(benzimidazol-2-yl) stilbene with ethylene oxide or with propylene oxide can be separated from one another by physical means, for example, recrystallization, to give the individual hydroxyethylated or hydroxypropylated 4,4-bis(benzimidazol-2- yl)stilbene in essentially pure form. From their intermediates, the individual quaternary benzimidazolium compounds can be prepared in essentially pure form by the methods disclosed herein. However, since all of the final products thus obtained are antibacterial and antifungal whitening and brightening agents, for many purposes there is no particular advantage in separating them and it is ordinarily preferred to use the mixtures of the quaternary benzimidazolium salts obtained as described in Examples 10B through 15B and 17 as such, without purification.

Following are representative results obtained when the compounds useful in the practice of this invention, which were prepared in accordance with the foregoing examples, were tested in vitro by standard serial dilution procedures for bacteriostatic (Bs), bactericidal (Bc), fungistatic (Fs), and fungicidal (Fc) properties; these results are expressed as minimum concentration of the test compound, in parts per million, required for no growth of the test organism. For example, in antibacterial tests, using Staphylococcus aureus 209, Salmonella typhosa Hopkins, Clostridium welchiz' M, and Pseudamonas aerugimosa 211, the results obtained were as follows:

desired quantity of an aqueous solution of an anionic or non-ionic detergent or of a laundry additive. The resulting fluorescent dispersions were used to dye white and colored natural synthetic fibers. All of the quaternary ammonium benzimidazolylstilbene products of the above examples were found to be substantive even from low concentrations, e.g. 0.000l%, in these aqueous media to white and colored fabrics of cotton, cellulose acetate, nylon, viscose rayon, polyacrylonitrile(Orlon-Du Font) and silk, thereby imparting a blue-white hue to the white fabrics and brightening the colored fabrics, while at the same time imparting an antibacterial and antifungal finish to the fabrics. Moreover, these products all had high stability to light as determied by exposure tests. In the solutions in detergents the products were substantially unaffected by a concentration of sodium hypochlorite of 0.2% by weight. The products useful in the practice of this invention were thus found to be especially useful as whitening and brightening agents to be used in conjunction with the laundering of white and colored fabrics.

A preferred mode of using and marketing these compounds is by incorporating them into solid or liquid detergents in a concentration of 0.02 to 0.5 percent of the whitening and brightening agent by weight. Although a concentration of less than 0.02 percent imparts an antibacterial and antifungal finish to the fabrics, the whitening and brightening effect at such concentrations is inadequate under ordinary laundering procedures. Moreover, a concentration higher than 0.5 percent is uneconomical and unnecessary since no increased whitening and brightening is effected at such higher concentrations.

The detergents which are employed are preferably water-soluble synthetic organic anionic and non-ionic detergents; these are of course well-known classes of Staphlococcus Salmonella Clostridium Pseudo nonas uurcus typhoaa welchz'z aerugzmosa Compound of Example Number Bs Bc BS 130 Bs Be Bs BC- 5. 50 500 1, 000 7. 75 500 1, 000 0. 5 7. 5 250 7. 5 25 500 1, 000 0. 75 25 75 250 1. 0 25 500 1, 000 0. 25 5. 0 2. 5 50 0. 5 5. 0 10 100 0. 25 75 50 100 0. 75 50 250 1, 000 150 500 50 250 500 5.0 500 750 1,000 500 1, 000 1, 000 1. 000 2. 5 75 1, 000 7. 5 50 750 1,000 0. 25 75 50 500 7. 5 100 1, 000 1, 000 0.50 25 50 500 7. 5 500 1, 000 1, 000 2. 5 50 50 1, 000 10 100 1, 000 1, 000 2. 5 40 400 500 25 250 500 500 1 5 2. 5 25 25 50 100 50 200 200 200 200 .1 200 In antifungal tests, using Trichopllyton menragl'ophyles, Aspergillus niger, and Monilia albicans as the test organisms, the following results were obtained:

DETERGENT COMPOSITIONS When the quaternary ammonium benzimidazolylstilbenes described in the foregoing examples were dispersed in aqueous media, the products in each instance fluoresced blue-white under ultraviolet light and showed a wide range of absorption in the ultraviolet region. Each of the products of these examples was dissolved in a suitable solvent, for instance, ethanol, 2-methoxyethanol or N,N-dimethylformamide, depending on the solubility characteristics of particular product, and the solution thus obtained was poured with vigorous stirring into the substances. Thus, for example there can be used organic sulfates and sulfonates, for instance sodium lauryl sulfate and sodium (higher alkyl)-benzenesulfonates; and polyoxyethylene ethers. These detergents are of course frequently available in admixture with each other or inorganic detergents and builders such as tetra-sodium pyrophosphate, sodium tripolyphosphate, sodium metasilicate, sodium borate, and sodium perborate, and these mixtures can also be employed in utilizing my invention.

The following examples are illustrative of the methods employed for incorporating all of the above examples of the quaternary benzimidazolium compounds into detergents and laundry additives. Other methods which will be readily apparent to those skilled in the art can be employed if desired.

Example 18 A solution of 0.15 g. of the product of Example 3 in ml. of N,N-dimethylformamide was diluted with water to 250 ml. A Launder-O-Meter (a standard laboratory washing machine of the American Association of Textile Chemists and Colorists, manufactured by Atlas Electric Devices, Chicago, Ill. and described in the Technical Manual and Year Book of the Association, Howes Publishing Co., Inc., New York, N.Y., volume XXVIII, 1952, pp. 82-83) jar was charged with 2.0 ml.

of the brightener solution and 53.5 ml. of a 0.4% solution of an alkyl aryl sulfonate detergent which initially contained no brightening agent. Then 51.5 ml. of tap water and two 5.0 gram swatches of cotton cloth were added to the jar. The Launder-O-Meter was run for twenty minutes at 120 F. The cloth was removed, rinsed for two minutes in cold running tap water and then ironed dry. The fabric thus treated had a brightness greater than that of the untreated sample. After laundering the fabric a total of six times according to this procedure, the fluorescence as measured by the fluorimeter, increased to approximately 300 percent of the fluorescent strength found on control cloths washed with the detergent solution described above but containing no quaternary ammonium brightening agent.

When the cloth samples thus treated with the quaternary ammonium flourescent compound of Example 3 were inoculated with a known number of bacteria and were then incubated at 37 C. for 18 to 24 hours, it was found that the viable Staphylococcus aureus 209 had been reduced by 97.5 percent as calculated by comparison with the control cloths.

Example 19 Following the procedure described in Example 18 hereinabove but substituting a non-ionic polyoxyethylene ether detergent initially containing no brightener for the anionic detergent used in that example and adding 0.4 ml. of a 5.25 percent aqueous solution of sodium hypochlorite, the fluorescence of the cotton samples after six launderings as measured by the fluorimeter was increased to approximately 400 percent of the fluorescent strength found on control cloths washed in the same detergent mixture but containing no quaternary ammonium brightener.

Moreover, when a known number of bacteria were placed on the cotton samples laundered as described above, and the number of viable bacteria determined after incubation at 37 C. for 18 to 24 hours, it was found that a 99 percent and a 94 percent reduction of Staphylococcus aureus 209 and Escherichia coli respectively had been elfected as calculated by comparison with the control cloths.

Example 20 A 3.5% solution of di-(hydrogenated tallow)dimethyl ammonium chloride was prepared by adding water heated to 75 C. to the molten material with vigorous agitation. The emulsion thus formed was heated on a steam bath for a period of fifteen minutes to effect complete solution. Then 0.25 ml. of the solution, 20 mg. of the product of Example dissolved in 2.0 ml. of ethanol, and distilled water to make a total volume of 200 ml. were added to a Launder-O-Meter jar. The sample containers were then placed in the water bath of the Launder-O-Meter and rotated for ten minutes at 100 F. Ten grams of unbleached cotton was then added to each jar. The jars were returned to the water bath and rotated for two minutes at 100 'F. The swatch was removed from the container, the excess solution was squeezed out and the cloth dried in a drum drier. This procedure imparted a blue-white fluorescence to the fabric.

The sample thus treated 'was evaluated for anti-bacterial effectiveness by the Agar Plate Method developed by the American Association of Textile Chemists and Colorists. When a 23 mm. diameter disc of the treated sample was placed on an agar plate that had previously been innoculated with Staphylococcus aureus 209 and then the entire incubated at 37 C. for 18 to 24 hours, a clear zone of inhibition 25 mm. in diameter was produced. Discs of control cloth, treated in the solution described above but containing no quaternary ammonium brightening agent, showed no zone of inhibitionwhen tested in the same manner.

14 Example 21 A Launder-O-Meter jar was charged with 53.5 ml. of a 0.4% aqueous solution of a non-ionic detergent (initially containing no brightener), 51.5 ml. of a 0.6% aqueous solution of a laundry additive, 2.0 ml. of a 0.04% aqueous solution of the product of Example 3 hereinabove and two five gram cotton swatches. The laundry additive used in this example was comprised of 98.4% of sodium tetraborate decahydrate, 0.4% of dodecyl benzene sulfonate and 1.2% of inert ingredient. No brightening agent was present initially in the laundry additive or the non-ionic detergent. The Launder-O-Meter was run for twenty minutes at 120 F.; the cloths were removed, washed for two minutes in cold, running tap water and then ironed dry. After a total of six launderings according to this procedure, the fluorescence increased to approximately 240 percent of the fluorescent strength found on cloth washed in the same solution but containing no quaternary ammonium brightener.

The cloth samples thus treated were inoculated with a known number of bacteria and were then incubated at 37 C. for 18 to 24 hours. It was found that viable Staphylococcus aureus 209 had been reduced by 97.4 percent and viable Escherichia coli had been reduced by 99.5 percent as calculated by comparison with the control cloths.

Example 22 To ml. of water there was added 5.0 ml. of a solution prepared by dissolving 10.0 g. of the product obtained in Example 12 in 100 ml. of alcohol 3-A and diluting the alcohol solution with water to a total volume of 1 liter. The solution was heated to 51 C. and a 1.76 g. sample of multifiber cloth 'was added and agitated at this temperature for twenty minutes. The cloth was removed, rinsed for two minutes with cold running tap water and then pressed dry between paper towels. All of the fibers contained in the swatch, viz. cellulose acetate, acrylonitrile-vinyl acetate copolymer (Acrilan- Chemstrand), cellulose triacetate (Arnel-Celanese), cotton, acrylonitrile esters copolymer (Creslan-American Cyanamid), poly(ethylene terephthalate) (Dacron- Du Pont), vinyl chloride-acrylonitrile copolymer (Dynel-Union Carbide), nylon, polyacrylonitrile (Orlon-Du Pont), silk viscose rayon, wool and acrylonitrile-vinyl acetate copolymer (Zefran-Dow) were beneficially whitened by this procedure. Exceptionally improved in brightness were the acrylonitrile-vinyl copolymer, the polyacrylonitrile, and the acrylonitrile-acrylic esters copolymer.

I claim:

1. A detergent composition consisting essentially of a detergent selected from the groupconsisting of watersoluble non-soap synthetic organic anionic detergents, and water-soluble synthetic organic non-ionic detergents, and dispersed therein 0.02 to 0.5 percent by weight of a compound having the structural formula where R R R and R are hydrogen, lower alkyl having 1 to 4 carbon atoms, lower alkoxy having 1 to 4 carbon atoms, or halo; Y and Y are lower alkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6 carbon atoms, 2-hydroxy-3-sulfopr0pyl, hydroxy-oxaalkyl having 3 to 15 carbon atoms, carboxy-lower alkyl having 2 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbon atoms, phenyl-lower alkyl having 7 to 11 carbon atoms, allyl or methallyl; Z and Z are lower alkyl having 1 to 6 carbon atoms, hydroxy-lower alkyl having 2 to 6 carbon atoms, carboxy-lower alkyl having 2 to 6 carbon atoms, cyano-lower alkyl having 2 to 6 carbon atoms, phenyl-lo'wer alkyl having 7 to 11 carbon atoms, allyl, methallyl, or 3-halo-2-propenyl; and An is an anion.

2. A detergent composition according to claim 1 consisting essentially of a water soluble synthetic organic non-ionic detergent and dispersed therein 0.02 to 0.5 percent by weight of a compound having the structural formula where Y and Y are each allyl; and Z and Z are lower alkyl having 1 to 6 carbon atoms, phenyl-lower alkyl having 7 to 11 carbon atoms, allyl or 3-halo-2-propenyl.

4. A detergent composition according to claim 1 consisting essentially of a water-soluble synthetic organic non-ionic detergent and dispersed therein 0102 to 0.5 percent by wcight of a compound having the structural formula where Y and Y are each hydroxy-oxaalkyl having 3 to 15 carbon atoms; and Z and Z are allyl or phenyl-lower alkyl having 7 to 11 carbon atoms.

5. A detergent composition according to claim 1 consisting essentially of a water-soluble synthetic organic anionic detergent and dispersed therein 0.02 to 0.5 percent by weight of a compound having the structural formula where Y and Y are each hydroxy-oxaalkyl having 3 to 15 carbon atoms; and Z and Z are allyl or phenyl-lower alkyl having 7 to 11 carbon atoms.

6. A detergent composition according to claim 1 consisting essentially of a water-soluble synthetic organic non-ionic detergent and dispersed therein 0.02 to 0.5 percent by weight of a compound having the structural formula where one of Y and Y is hydroxy-lower alkyl having 2 F to 6 carbon atoms and the other is hydroxy-oxaalkyl having 3 to 15 carbon atoms; and Z and Z are phenyl-lower alkyl having 7 to ll carbon atoms.

7. A detergent composition according to claim 1 consisting essentially of a water-soluble synthetic organic anionic detergent and dispersed therein 0.02 to 0.5 per- 17 cent by weight of a compound having the structural formula Z1 l a;

where Y and Y are each hydroxy-lower alkyl; and Z and Z are each phenyl-lower alkyl.

9. A detergent composition according to claim 1 consisting essentially of a water-soluble synthetic organic anionic detergent and dispersed therein 0.02 to 0.5 percent by weight of a compound having the structural formula where 1 and Y are each hydroXy-lower alykl; and Z and Z are each phenyl-lower alkyl.

10. A detergent composition according to claim 1 consisting essentially of a detergent selected from the group consisting of water-soluble non-soap synthetic organic anionic detergents, and water-soluble synthetic organic non-ionic detergents, and dispersed therein 0.02 to 0.5 percent by weight of a compound having the structural formula where each of Y Y Z and Z is allyl.

References Cited UNITED STATES PATENTS 2,808,407 10/1957 Ackermann et a1. 260-240 2,838,504 6/ 1958 Crounse 260240 2,878,248 3/ 1959 Crounse 260240 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 

